CN107346824B - Preparation method and application of gradient ternary cathode material - Google Patents
Preparation method and application of gradient ternary cathode material Download PDFInfo
- Publication number
- CN107346824B CN107346824B CN201710390520.1A CN201710390520A CN107346824B CN 107346824 B CN107346824 B CN 107346824B CN 201710390520 A CN201710390520 A CN 201710390520A CN 107346824 B CN107346824 B CN 107346824B
- Authority
- CN
- China
- Prior art keywords
- nickel
- cobalt
- solution
- manganese
- gradient
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of lithium ion battery anode materials, and particularly discloses a preparation method and application of a gradient ternary anode material. The preparation method of the gradient ternary cathode material is characterized by comprising the following steps: preparing a nickel-cobalt-manganese salt solution 1, a nickel-cobalt-manganese salt solution 2, an ammonia water solution and a precipitator solution; adding an ammonia water solution and deionized water into the reaction kettle, and uniformly mixing; under the mechanical stirring, uniformly mixing the nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 through a pipeline mixer, adding the mixture into a reaction kettle, and continuously adding a precipitator solution and an ammonia water solution to perform coprecipitation reaction; after the reaction is finished, separating, washing and drying to obtain a gradient precursor material; and uniformly mixing the gradient precursor material with lithium salt, presintering, and then preserving heat to obtain the product. The invention adopts programmed control, has high automation degree and accurate process control, can ensure controllable component gradient and controllable particle size distribution of the material particles, and improves the batch uniformity of the material.
Description
(I) technical field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a preparation method and application of a gradient ternary anode material.
(II) background of the invention
The lithium ion battery is a novel secondary battery, and has obvious advantages of high specific energy, long cycle life, good discharge stability, small environmental pollution, large development potential and the like, so the lithium ion battery is a key direction for development of the global energy industry. The ternary cathode material has the characteristics of high energy density, relatively low cost, excellent cycle performance and the like, becomes one of the most promising potential and development prospects in various cathode materials, and is widely applied to the fields of consumer products, digital products, power products, unmanned aerial vehicles and the like. The high-nickel anode material is favored by people due to the characteristic of high specific capacity.
High-nickel ternary positive electrode materialHigh specific capacity of the material, but poor structural stability, and high Ni concentration during charging4+The existence of (2) makes the material safety and the cycling stability not meet the commercialization requirements. In order to improve the capacity of the lithium battery and simultaneously consider the safety problem of the battery, the preparation of the high-nickel positive electrode material with concentration gradient becomes a means for overcoming the defects of the high-nickel material.
The patent CN104409716A provides a method for preparing a cathode material with a concentration gradient, in which a coprecipitation method is used to synthesize a material precursor with high nickel content, then a ternary material solution with low content is coprecipitated outside the material precursor with high nickel content to obtain a composite precursor, and then the composite precursor is sintered to obtain the cathode material of a high nickel lithium ion battery. The method realizes a gradient structure by a coating method, the coating uniformity is difficult to ensure, and meanwhile, the jumping property of core and shell element components is large, so that the structural stability is influenced.
The patent CN104201369B provides a preparation method of a precursor of a gradient anode material of a lithium ion battery, which comprises the specific steps of preparing two solutions A and B with different molar ratios from nickel salt, cobalt salt and manganese salt, wherein the volumes of the solutions are the same; and gradually adding the solution A into the solution B by adopting a metering pump, adding the uniformly mixed solution into a reaction kettle in the process, simultaneously adding an alkali solution and a complexing agent solution into the reaction kettle, stabilizing synthesis process parameters in the reaction process, stopping the reaction when the solution A, B is completely consumed simultaneously, and finally centrifugally washing and drying to obtain the spherical anode material precursor with various elements in different concentration gradient distribution. The method realizes continuous change of the components, but the gradient solution formed by the method is gradually reduced at first and then is sharply reduced, and uniform change of the components of the material particles is difficult to realize.
Disclosure of the invention
The invention provides a preparation method and application of a gradient ternary cathode material with high automation degree, accurate process control and high product uniformity to make up the defects of the prior art.
The invention is realized by the following technical scheme:
a preparation method of a gradient ternary cathode material comprises the following steps:
(1) preparing a nickel-cobalt-manganese salt solution 1, a nickel-cobalt-manganese salt solution 2, an ammonia water solution and a precipitator solution, and introducing inert gas to remove oxygen;
(2) adding an ammonia water solution and deionized water into the reaction kettle, uniformly mixing, and introducing inert gas to remove oxygen;
(3) under mechanical stirring, respectively using a pump to drive the stirrer to rotate at a speed of V1And V2The nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are extracted at the speed of (1), are converged into a pipeline with a pipeline mixer, are added into a reaction kettle after being uniformly mixed by the pipeline mixer, and are continuously added with a precipitator solution and an ammonia water solution, the pH value of the solution in the reaction kettle and the ammonia water concentration are controlled to be Cmol/L, the reaction temperature is 40-60 ℃, and a coprecipitation reaction is carried out under the protection of inert gas;
(4) after the reaction is finished, the gradient precursor material is obtained through separation, washing and drying, and the average molecular formula of the gradient precursor material is NixCo1-x-yMny(OH)2Wherein x is more than 0.5 and less than 1, y is more than 0 and less than 0.5, and x + y is less than 1;
(5) uniformly mixing the gradient precursor material with lithium salt, heating to 450-550 ℃ at the speed of 2-5 ℃/min in an aerobic atmosphere, presintering for 4-6h, then heating to 600-900 ℃ at the speed of 2-5 ℃/min, and preserving heat for 10-20h to obtain the gradient ternary cathode material LiNixCo1-x-yMnyO2。
The more preferable technical scheme of the invention is as follows:
in the step (1), the molar ratio of the nickel, cobalt and manganese in the nickel, cobalt and manganese salt solution 1 is a1：1-a1-b1：b1Wherein, 0.3 < a1＜0.6，0.1＜b1＜0.3，a1+b1Less than 1; the molar ratio of the nickel, the cobalt and the manganese in the nickel, the manganese and the manganese salt solution 2 is a2：1-a2-b2：b2Wherein, 0.6 < a2＜1，0≤b2＜0.2，a2+b2Less than 1; the molar concentrations of the nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are the same, and the range is 1-4 mol/L; the concentration of the precipitant solution is 4-10 mol/L.
The nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are one or more of nitrate, sulfate, chloride and acetate solutions of nickel, cobalt and manganese; the precipitant solution is one or more of sodium carbonate, sodium bicarbonate, potassium hydroxide or sodium hydroxide aqueous solution.
In the steps (1), (2) and (3), the inert gas is one or two of nitrogen and argon.
In step (3), V1And V2The value of (A) is continuously changed along with the reaction time t, and is a continuous function of the reaction time t, and the molar ratio a of nickel element in the nickel-cobalt-manganese salt solution added into the reaction kettle at the time t is changed along with the reaction time t in an arbitrary continuous gradient manner, wherein a = (V)1*a1+V2*a2）/（V1+V2) And a is more than 0.3 and less than 1.
The pH value of the solution in the reaction kettle, the concentration C of ammonia water and the molar ratio a of nickel element in the nickel-cobalt-manganese salt solution added into the reaction kettle at the moment of reaction time t are in linear positive correlation, the pH = f (a), the concentration C = psi (a), the pH is more than 9 and less than 12, and the C is more than 0.3 and less than 2; preferably, the pH value of the solution in the reaction kettle is continuously and gradually changed, and the maximum fluctuation amplitude is less than 0.05.
In the step (5), the addition amounts of the gradient precursor material and the lithium salt satisfy: the molar ratio of the total mole of nickel, cobalt and manganese in the gradient precursor material to the mole of the lithium source is 1: 1.02-1.1.
The gradient ternary cathode material obtained by the preparation method is applied as a cathode material of a lithium battery.
The preparation of the precursor adopts a coprecipitation method, the components of the nickel-cobalt-manganese solution are accurately controlled to be in continuous gradient change along with any curve by a program, meanwhile, an online ammonia measuring instrument and an online pH meter are adopted for reaction, the pH value and the ammonia water concentration in the reaction process are accurately controlled, the molar ratio of the ammonia water to nickel ions in the nickel-cobalt-manganese mixed solution injected into a reaction kettle is correspondingly gradually changed, and the continuous gradient distribution of three elements of nickel-cobalt-manganese in the precursor from inside to outside is realized, so that the nonuniformity of materials in the aspects of volume effect, stress and the like caused by the mutation of the components is greatly reduced, the microcrack and the breakage of particles in the charging and discharging process are reduced, and the circulation stability is improved.
The invention adopts programmed control, has high automation degree and accurate process control, can ensure controllable component gradient and controllable particle size distribution of the material particles, and improves the batch uniformity of the material.
(IV) description of the drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is an EDS energy spectrum of a gradient precursor obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a gradient precursor obtained in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the gradient ternary cathode material obtained in example 1 of the present invention;
FIG. 4 is an XRD pattern of the gradient ternary cathode material obtained in example 1 of the present invention;
FIG. 5 is a charge-discharge curve diagram of the gradient ternary cathode material obtained in example 1 of the present invention;
fig. 6 is a graph of cycle testing of the gradient ternary cathode material obtained in example 1 of the present invention.
(V) detailed description of the preferred embodiments
Example 1:
the preparation method of the gradient ternary cathode material comprises the following steps:
(1) preparing 20L of 2mol/L nickel-cobalt-manganese salt solution 1, wherein the molar ratio of three elements of nickel, cobalt and manganese is Ni: co: mn =6:1:3 and 40L 2mol/L of nickel cobalt manganese salt solution 2, wherein the molar ratio of three elements of nickel cobalt manganese is Ni: co: mn =9:1: 0; preparing 4mol/L ammonia water solution and 8mol/L precipitator solution, and introducing inert gas to remove oxygen;
(2) adding an ammonia water solution and deionized water into a reaction kettle, uniformly mixing to ensure that the initial concentration of the ammonia water in the reaction kettle is 1mol/L, and introducing inert gas to remove oxygen;
(3) setting V on programmable logic controller1And V2As a function of the reaction time t, under mechanical stirring, the reaction time t is measured as V1And V2The nickel cobalt manganese salt solution 1 and the nickel cobalt manganese salt solution 2 are extracted at the speed of (1), are converged into a pipeline with a pipeline mixer and are mixed through the pipelineAfter being mixed uniformly, the mixture is added into a reaction kettle, wherein the molar ratio a of the initial nickel element in the nickel-cobalt-manganese salt solution added into the reaction kettleStarting point0.9, the molar ratio of the nickel element a at the end of the reactionFinal (a Chinese character of 'gan')Is 0.6; continuously adding a precipitator solution and an ammonia water solution, and controlling the pH value of the solution in the reaction kettle to be pH, wherein the initial pH valueStarting pointIs 12.0, and the pH value is adjusted at the end of the reactionFinal (a Chinese character of 'gan')Is 11.5 and satisfies the functional formula pH = f (a); controlling the concentration of ammonia water in the reaction kettle to be Cmol/L, wherein C is 1mol/L at first, and C is 0.4mol/L at last, and C = psi (a); the reaction temperature is 40-60 ℃, and coprecipitation reaction is carried out under the protection of inert gas, so as to finally obtain a gradient precursor material;
(4) separating, washing and drying to obtain a gradient precursor material with an average molecular formula of Ni0.8Co0.1Mn0.1(OH)2；
(5) Uniformly mixing the gradient precursor material and lithium salt in a molar ratio of 1:1.08, heating to 550 ℃ at a speed of 5 ℃/min in an aerobic atmosphere, presintering for 6h, heating to 800 ℃ at a speed of 5 ℃/min, and keeping the temperature for 12h to obtain the gradient cathode material LiNi0.8Co0.1Mn0.1O2。
The ternary cathode material LiNi obtained in this example0.8Co0.1Mn0.1O2The button cell is prepared as the anode material, and the electrochemical performance of the button cell is tested by adopting a blue-electricity system, the test voltage range is 2.7-4.3V, and the results are shown in figures 5 and 6.
Example 2:
the preparation method of the gradient ternary cathode material comprises the following steps:
(1) preparing 10L of 2mol/L nickel-cobalt-manganese salt solution 1, wherein the molar ratio of three elements of nickel, cobalt and manganese is Ni: co: mn =4:1.5:4.5 and 30L of 2mol/L nickel cobalt manganese salt solution 2, wherein the molar ratio of three elements of nickel cobalt manganese is Ni: co: mn =8:1.5: 0.5; preparing 4mol/L ammonia water solution and 8mol/L precipitator solution, and introducing inert gas to remove oxygen;
(2) adding an ammonia water solution and deionized water into the reaction kettle, uniformly mixing to ensure that the initial concentration of the ammonia water in the reaction kettle is 0.9mol/L, and introducing inert gas to remove oxygen;
(3) setting V on programmable logic controller1And V2As a function of the reaction time t, under mechanical stirring, the reaction time t is measured as V1And V2The nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are extracted at the speed, are converged into a pipeline with a pipeline mixer, are uniformly mixed by the pipeline mixer and are added into a reaction kettle, wherein the molar ratio a of the initial nickel element in the nickel-cobalt-manganese salt solution added into the reaction kettleStarting point0.8, the molar ratio of the nickel element a at the end of the reactionFinal (a Chinese character of 'gan')Is 0.4; continuously adding a precipitator solution and an ammonia water solution, and controlling the pH value of the solution in the reaction kettle to be pH, wherein the initial pH valueStarting pointpH at the end of the reaction was 11.8Final (a Chinese character of 'gan')Is 11.3 and satisfies the functional formula pH = f (a); controlling the concentration of ammonia water in the reaction kettle to be Cmol/L, wherein C is 0.9mol/L at first, C is 0.3mol/L at last, and C = psi (a); the reaction temperature is 40-60 ℃, and coprecipitation reaction is carried out under the protection of inert gas, so as to finally obtain a gradient precursor material;
(4) separating, washing and drying to obtain a gradient precursor material with an average molecular formula of Ni0.7Co0.15Mn0.15(OH)2；
(5) Uniformly mixing the gradient precursor material and lithium salt in a molar ratio of 1:1.08, heating to 550 ℃ at a speed of 5 ℃/min in an aerobic atmosphere, presintering for 6h, heating to 820 ℃ at a speed of 5 ℃/min, and preserving heat for 12h to obtain the gradient cathode material LiNi0.7Co0.15Mn0.15O2。
Example 3:
the preparation method of the gradient ternary cathode material comprises the following steps:
(1) preparing 30L of 2mol/L nickel-cobalt-manganese salt solution 1, wherein the molar ratio of nickel, cobalt and manganese is Ni: co: 2, Mn =5:2:3 and 15L 2mol/L of nickel-cobalt-manganese salt solution 2, wherein the molar ratio of three elements of nickel-cobalt-manganese is Ni: co: mn =8:2: 0; preparing 4mol/L ammonia water solution and 8mol/L precipitator solution, and introducing inert gas to remove oxygen;
(2) adding an ammonia water solution and deionized water into the reaction kettle, uniformly mixing to ensure that the initial concentration of the ammonia water in the reaction kettle is 0.85mol/L, and introducing inert gas to remove oxygen;
(3) setting V on programmable logic controller1And V2As a function of the reaction time t, under mechanical stirring, the reaction time t is measured as V1And V2The nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are extracted at the speed, are converged into a pipeline with a pipeline mixer, are uniformly mixed by the pipeline mixer and are added into a reaction kettle, wherein the molar ratio a of the initial nickel element in the nickel-cobalt-manganese salt solution added into the reaction kettleStarting point0.8, the molar ratio of the nickel element a at the end of the reactionFinal (a Chinese character of 'gan')Is 0.5; continuously adding a precipitator solution and an ammonia water solution, and controlling the pH value of the solution in the reaction kettle to be pH, wherein the initial pH valueStarting pointpH at the end of the reaction was 11.8Final (a Chinese character of 'gan')Is 11.3 and satisfies the functional formula pH = f (a); controlling the concentration of ammonia water in the reaction kettle to be Cmol/L, wherein C is 0.85mol/L at first, and C is 0.4mol/L at last, and C = psi (a); the reaction temperature is 40-60 ℃, and coprecipitation reaction is carried out under the protection of inert gas, so as to finally obtain a gradient precursor material;
(4) separating, washing and drying to obtain a gradient precursor material with an average molecular formula of Ni0.6Co0.2Mn0.2(OH)2；
(5) Uniformly mixing the gradient precursor material and lithium salt in a molar ratio of 1:1.08, heating to 550 ℃ at a speed of 5 ℃/min in an aerobic atmosphere, presintering for 6h, heating to 850 ℃ at a speed of 5 ℃/min, and keeping the temperature for 12h to obtain the gradient cathode material LiNi0.6Co0.2Mn0.2O2。
Claims (8)
1. The preparation method of the gradient ternary cathode material is characterized by comprising the following steps of:
(1) preparing a nickel-cobalt-manganese salt solution 1, a nickel-cobalt-manganese salt solution 2, an ammonia water solution and a precipitator solution, and introducing inert gas to remove oxygen;
(2) adding an ammonia water solution and deionized water into the reaction kettle, uniformly mixing, and introducing inert gas to remove oxygen;
(3) under mechanical stirring, respectively using a pump to drive the stirrer to rotate at a speed of V1And V2The nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are extracted at the speed of (1), are converged into a pipeline with a pipeline mixer, are added into a reaction kettle after being uniformly mixed by the pipeline mixer, and are continuously added with a precipitator solution and an ammonia water solution, the pH value of the solution in the reaction kettle and the ammonia water concentration are controlled to be Cmol/L, the reaction temperature is 40-60 ℃, and a coprecipitation reaction is carried out under the protection of inert gas;
wherein, V1And V2The value of (A) is continuously changed along with the reaction time and is a continuous function of the reaction time t, and the molar ratio a of nickel element to nickel, cobalt and manganese in the nickel-cobalt-manganese salt solution added into the reaction kettle at the time t is changed along with the reaction time t in an arbitrary continuous gradient manner, wherein the a is (V)1*a1+V2*a2)/(V1+V2) A is more than 0.3 and less than 1, a1 is the molar ratio of nickel element to nickel, cobalt and manganese in the nickel-cobalt-manganese salt solution 1, and a2 is the molar ratio of nickel element to nickel, cobalt and manganese in the nickel-cobalt-manganese salt solution 2;
the pH value of the solution in the reaction kettle, the concentration C of ammonia water and the molar ratio a of nickel element to nickel, cobalt and manganese in the nickel-cobalt-manganese salt solution added into the reaction kettle at the moment t are in linear positive correlation, wherein the pH is f (a), the C is psi (a), the pH is more than 9 and less than 12, and the C is more than 0.3 and less than 2;
accurately controlling the components of the nickel-cobalt-manganese solution to be in continuous gradient change along with time in an arbitrary curve by a program, and simultaneously accurately controlling the pH value and the ammonia water concentration in the reaction process to ensure that the molar ratio a of nickel ions to nickel-cobalt-manganese in the nickel-cobalt-manganese mixed solution injected into the reaction kettle is correspondingly gradually changed, so as to realize the continuous gradient distribution of the nickel-cobalt-manganese three elements in the precursor from inside to outside;
(4) after the reaction is finished, the gradient precursor material is obtained through separation, washing and drying, and the average molecular formula of the gradient precursor material is NixCo1-x-yMny(OH)2Wherein x is more than 0.5 and less than 1, y is more than 0 and less than 0.5, and x + y is less than 1;
(5) uniformly mixing the gradient precursor material with lithium salt, heating to 450-550 ℃ at the speed of 2-5 ℃/min in an aerobic atmosphere, presintering for 4-6h, then heating to 600-900 ℃ at the speed of 2-5 ℃/min, and preserving heat for 10-20h to obtain the gradient ternary cathode material LiNixCo1-x-yMnyO2。
2. The method for preparing a gradient ternary cathode material according to claim 1, wherein: in the step (1), the molar ratio of the nickel, cobalt and manganese in the nickel, cobalt and manganese salt solution 1 is a1：1-a1-b1：b1Wherein, 0.3 < a1＜0.6，0.1＜b1＜0.3，a1+b1Less than 1; the molar ratio of the nickel, the cobalt and the manganese in the nickel, the manganese and the manganese salt solution 2 is a2：1-a2-b2：b2Wherein, 0.6 < a2＜1，0≤b2＜0.2，a2+b2Less than 1; the molar concentrations of the nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are the same, and the range is 1-4 mol/L; the concentration of the precipitant solution is 4-10 mol/L.
3. The method for preparing a gradient ternary cathode material according to claim 1, wherein: in the step (1), the nickel-cobalt-manganese salt solution 1 and the nickel-cobalt-manganese salt solution 2 are one or more of nitrate, sulfate, chloride and acetate solutions of nickel, cobalt and manganese.
4. The method for preparing a gradient ternary cathode material according to claim 1, wherein: in the step (1), the precipitant solution is one or more of potassium hydroxide or sodium hydroxide aqueous solution.
5. The method for preparing a gradient ternary cathode material according to claim 1, wherein: in the steps (1), (2) and (3), the inert gas is argon.
6. The method for preparing a gradient ternary cathode material according to claim 1, wherein: in the step (5), the molar ratio of the total mole of nickel, cobalt and manganese in the gradient precursor material to the mole of the lithium source is 1: 1.02-1.1.
7. The method for preparing a gradient ternary cathode material according to claim 1, wherein: the pH value of the solution in the reaction kettle is continuously and gradually changed, and the maximum fluctuation amplitude is less than 0.05.
8. The application of the gradient ternary cathode material obtained by the preparation method according to claim 1 as a cathode material of a lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710390520.1A CN107346824B (en) | 2017-05-27 | 2017-05-27 | Preparation method and application of gradient ternary cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710390520.1A CN107346824B (en) | 2017-05-27 | 2017-05-27 | Preparation method and application of gradient ternary cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107346824A CN107346824A (en) | 2017-11-14 |
| CN107346824B true CN107346824B (en) | 2020-06-09 |
Family
ID=60254419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710390520.1A Active CN107346824B (en) | 2017-05-27 | 2017-05-27 | Preparation method and application of gradient ternary cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107346824B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109962233A (en) * | 2017-12-25 | 2019-07-02 | 格林美（无锡）能源材料有限公司 | A kind of class monocrystalline positive electrode of gradient type and preparation method thereof |
| KR102008875B1 (en) * | 2017-12-26 | 2019-08-08 | 주식회사 포스코 | Aparatus for manufacturing precursor with graded concentration and scheduling method of supplying base material |
| CN108598466A (en) * | 2018-05-08 | 2018-09-28 | 哈尔滨工业大学（威海） | A kind of preparation method for the nickel-cobalt-manganese ternary material for making constituent content distribution gradient |
| CN109301240A (en) * | 2018-10-21 | 2019-02-01 | 圣戈莱（北京）科技有限公司 | Nickelic multicomponent material presoma of cation doping gradient and its preparation method and application |
| CN109244454B (en) * | 2018-11-06 | 2021-04-02 | 北京理工大学 | NCM ternary cathode material with hierarchical structure |
| CN112002878A (en) * | 2019-05-27 | 2020-11-27 | 湖北万润新能源科技发展有限公司 | Preparation method of ternary gradient material with manganese-rich surface layer |
| CN110391416A (en) * | 2019-07-11 | 2019-10-29 | 光鼎铷业(广州)集团有限公司 | A kind of rubidium doping concentration gradient tertiary cathode material and preparation method thereof |
| CN110589902A (en) * | 2019-07-23 | 2019-12-20 | 河南科隆新能源股份有限公司 | Preparation method of composite cladding doped nickel-cobalt-manganese precursor material |
| CN110534714A (en) * | 2019-08-14 | 2019-12-03 | 江苏海基新能源股份有限公司 | A kind of preparation method of full gradient tertiary cathode material |
| CN110492098A (en) * | 2019-09-05 | 2019-11-22 | 中伟新材料有限公司 | The preparation method of nickel-cobalt lithium manganate cathode material and preparation method thereof and its presoma |
| CN111732131B (en) * | 2020-06-29 | 2021-12-03 | 电子科技大学 | Preparation method of core-shell structure ternary cathode material |
| CN112164784B (en) * | 2020-08-27 | 2022-04-08 | 荆门市格林美新材料有限公司 | Quaternary concentration gradient core-shell lithium ion battery positive electrode material and preparation method thereof |
| CN114804224A (en) * | 2021-01-29 | 2022-07-29 | 微宏动力系统（湖州）有限公司 | Preparation method of positive electrode material precursor, positive electrode material and battery |
| CN113023795A (en) * | 2021-05-24 | 2021-06-25 | 昆山宝创新能源科技有限公司 | Multi-element positive electrode precursor and preparation method and application thereof |
| CN113540436A (en) * | 2021-06-10 | 2021-10-22 | 中南大学 | Tungsten ion doped high nickel gradient ternary positive electrode material and preparation method thereof |
| CN114229919A (en) * | 2021-12-20 | 2022-03-25 | 湖北亿纬动力有限公司 | Gradient ternary precursor, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514411A (en) * | 2015-12-19 | 2016-04-20 | 山东玉皇新能源科技有限公司 | Synthesis method of positive electrode material for lithium ion batteries |
| CN105609759A (en) * | 2016-03-25 | 2016-05-25 | 中国科学院长春应用化学研究所 | High-nickel-series and full-concentration gradient lithium ion battery positive electrode material and preparation method thereof |
| CN106207138A (en) * | 2016-09-20 | 2016-12-07 | 中国科学院化学研究所 | A kind of method for preparing anode material of lithium-ion battery and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2634148B1 (en) * | 2012-03-01 | 2015-04-01 | GS Yuasa International Ltd. | Active material for non-aqueous electrolyte secondary battery, method for production of the active material, electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| KR101702572B1 (en) * | 2014-08-22 | 2017-02-13 | 주식회사 포스코이에스엠 | Manufacturing method of cobalt free concentration gradient cathod active material and cobalt free concentration gradient cathod active material made by the same |
-
2017
- 2017-05-27 CN CN201710390520.1A patent/CN107346824B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105514411A (en) * | 2015-12-19 | 2016-04-20 | 山东玉皇新能源科技有限公司 | Synthesis method of positive electrode material for lithium ion batteries |
| CN105609759A (en) * | 2016-03-25 | 2016-05-25 | 中国科学院长春应用化学研究所 | High-nickel-series and full-concentration gradient lithium ion battery positive electrode material and preparation method thereof |
| CN106207138A (en) * | 2016-09-20 | 2016-12-07 | 中国科学院化学研究所 | A kind of method for preparing anode material of lithium-ion battery and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107346824A (en) | 2017-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107346824B (en) | Preparation method and application of gradient ternary cathode material | |
| CN108878818B (en) | Core-shell structure nickel-cobalt-manganternary ternary anode material presoma and preparation method thereof | |
| CN108217753B (en) | Gradient doped cobaltosic oxide material and preparation method thereof | |
| CN107565121B (en) | Preparation method of modified positive electrode material of lithium battery | |
| CN110034297A (en) | A kind of nickelic lithium ion anode material and preparation method thereof | |
| CN107123792B (en) | Ternary cathode material with double-layer composite structure and preparation method thereof | |
| CN103715424A (en) | Core-shell structured cathode material and preparation method thereof | |
| CN104733724A (en) | Positive electrode material for high-nickel lithium ionic secondary battery and preparation method thereof | |
| CN107910531A (en) | A kind of preparation method of high Ni-based tertiary cathode material | |
| CN110085858A (en) | A kind of nickelic tertiary cathode material of niobium-phosphor codoping and its preparation method and application | |
| CN113540436A (en) | Tungsten ion doped high nickel gradient ternary positive electrode material and preparation method thereof | |
| CN108767216A (en) | Anode material for lithium-ion batteries and its synthetic method with the full concentration gradient of variable slope | |
| CN105633384B (en) | Power lithium-ion battery positive electrode surface modification technology method | |
| CN109411718A (en) | The preparation method of the tertiary cathode material of doping vario-property | |
| CN112830527B (en) | Precursor of hollow cathode material and preparation method thereof | |
| CN107482172A (en) | A kind of high-rate type stratiform lithium-rich manganese-based anode material and preparation method thereof | |
| CN109704411A (en) | Nickel lithium manganate cathode material and preparation method thereof | |
| CN110589902A (en) | Preparation method of composite cladding doped nickel-cobalt-manganese precursor material | |
| CN113644272A (en) | Cerium-bismuth composite oxide doped lithium ion battery positive electrode material and preparation method thereof | |
| CN103606675A (en) | Preparation method of metallic-ion-doped lithium-nickel-cobalt-oxygen positive pole material | |
| CN112164783A (en) | Lithium battery positive electrode material and preparation method thereof | |
| CN113571694B (en) | Multi-ion modified ternary material precursor and preparation method of anode material | |
| CN113387401B (en) | Preparation method of scandium-tungsten doped anode material precursor | |
| CN112582587A (en) | Core-shell structure high-nickel cathode material with single crystal as core and preparation method thereof | |
| CN106328936A (en) | Preparation method of coated spherical nickel-cobalt-aluminum precursor, and preparation method of nickel-cobalt-lithium aluminate pole materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |